Flexible thermoplastic epoxy resin and coatings prepared therefrom

ABSTRACT

Flexible thermoplastic epoxy resins are prepared by reacting (1) an advanced epoxy resin prepared by reacting a mixture of an aromatic based epoxy resin and an aliphatic based epoxy resin with a polyhydric phenol in the presence of an advancement catalyst with (2) a monocarboxylic acid or anhydride thereof; reacting the resultant product with a mixture of an armotic based epoxy resin and a monofunctional material reactive with vicinal epoxy groups; and reacting the resultant product with a carboxyl terminated elastomer. These resins are particularly useful in formulating pavement marking paints.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 024,748, filed Mar. 11,1987, now U.S. Pat. No. 4,755,542.

FIELD OF THE INVENTION

The present invention pertains to thermoplastic epoxy resins andcoatings prepared therefrom.

BACKGROUND OF THE INVENTION

Thermoplastic (non-thermoset) epoxy resins have been employed in theformulation of highway pavement marking paints as disclosed by J. M.Dale in Development of Lane Delineation With Improved Durablity, ReportNo. FHWA-BD-75-70 July 1975, available from U.S. Dept. of Trans. Off. ofDev., Federal Hwy. Adms., Wash. D.C., 20590. The paint formulations aremaintained at elevated temperatures, usually 450° F. to 500° F., duringapplication. While they provide an excellent highway marking paint interms of abrasive resistance, they are deficient in terms ofapplicability since they exhibit a substantial increase in viscositywhile being maintained at the application temperature. Even if thethermoplastic epoxy resins could maintain its viscosity, the resultingthermoplastic epoxy resins do not have the necessary flexibility toallow wide-spread use.

It would be desirable to have a thermoplastic (non-thermoset) epoxyresin which exhibits a much reduced viscosity increase at elevatedtemperatures, i.e. it is more thermally stable and exhibits improvedflexibility over those thermoplastic epoxy resins disclosed by J. M.Dale. It is desirable that the flexibility of the formulatedthermoplastic resin for use in highway marking paints be at least about15 percent.

SUMMARY OF THE INVENTION

The present invention pertains to a thermally stable, flexiblethermoplastic epoxy resin resulting from

(A) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and an aromatichydroxyl group, a mixture comprising

(1) at least one aromatic based epoxy resin having an average of morethan 1 but not more than about 2.1 vicinal epoxy groups per molecule;

(2) at least one aliphatic based epoxy resin having an average of morethan 1 but not more than about 2.1 vicinal epoxy groups per molecule;

(3) at least one material having an average of more than 1 but not morethan about 2 phenolic hydroxyl groups per molecule;

wherein components (1) and (2) are employed in quantities such that fromabout 90 to about 99.6, suitably from about 94 to about 99.6, moresuitably from about 96 to about 99.6, percent of the vicinal epoxygroups are contributed by the aromatic based epoxy resin and from about10 to about 0.4, suitably from about 6 to about 0.4, more suitably fromabout 4 to about 0.4, percent of the vicinal epoxy groups arecontributed by the aliphatic based epoxy resin; and wherein component(3) is employed in quantities such that the resultant product has anepoxide equivalent weight (EEW) of from about 1600 to about 2500,suitably from about 1650 to about 2100, more suitably from about 1700 toabout 1900, calculated on the basis that the aromatic groups containedtherein are free of substituent groups even if they do in fact containsubstituent groups:

(B) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a carboxylgroup, the product resulting from (A) with

(4) at least one aromatic or aliphatic monocarboxylic acid in a quantitywhich provides a ratio of moles of component (4) per epoxide groupcontained in component (1) of from about 0.033:1 to about 0.2:1,suitably from about 0.037:1 to about 0.1:1, more suitably from about0.038:1 to about 0.07:1;

(C) optionally, reacting, in the presence of an effective quantity of acatalyst for effecting the reaction between a vicinal epoxide group anda group selected from --OH, --SH, --COOH and --CO--O--CO-- groups, theproduct resulting from (B) with a mixture comprising

(5) an aromatic based epoxy resin having an average of more than 1 butnot more than about 2.1 vicinal epoxy groups per molecule and an EEW ofnot greater than about 225, suitably not greater than about 200, moresuitably not greater than about 195, calculated on the basis of thearomatic groups being free of substituent groups whether or not they doin fact contain substituent groups; and

(6) a reactant material having only one group per molecule which isreactive with a vicinal epoxy group selected from --OH, --SH, --COOH and--CO--O--CO-- groups;

wherein component (5) is employed in an amount which provides a ratio ofvicinal epoxy groups from component (5) to the combined amount epoxygroups contained in components (1) and (2) of from about 0.42:1 to about0.48:1, suitably from about 0.43:1 to about 0.47:1, more suitably fromabout 0.44:1 to about 0.46:1: and component (6) is employed in an amountwhich provides from about 0.87 to about 1, suitably from about 0.96 toabout 1, more suitably from about 0.98 to about 1, group reactive with avicinal epoxy group per combined vicinal epoxy group contained in theproduct from (B) and component (5); and

(D) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a carboxylgroup, the product resulting from (C) with

(7) a carboxyl terminated elastomer in an amount which provides a ratioof carboxyl groups to combined vicinal epoxy groups contained incomponents (1) and (2) of from about 0.0028:1 to about 0.03:1, suitablyfrom about 0.003:1 to about 0.009:1, more suitably from about 0.0035:1to about 0.008:1;

with the proviso that (a) the combined quantity of groups reactive withan epoxide group from components (3), (4), (6) and (7) cannot exceed thecombined quantity of epoxide groups contained in components (1), (2) and(5) and (b) if step (C) is not performed, then step (D) is conductedemploying the product from step (B) instead of that from step (C).

Another aspect of the present invention pertains to a mixture comprising

(I) from about 70 to about 95, suitably from about 80 to about 95, moresuitably from about 84 to about 94 percent by weight based upon thecombined weight of components (I) and (II) of a thermally stable,flexible thermoplastic epoxy resin resulting from

(A) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and an aromatichydroxyl group, a mixture comprising

(1) at least one aromatic based epoxy resin having an average of morethan 1 but not more than about 2.1 vicinal epoxy groups per molecule;

(2) at least one aliphatic based epoxy resin having an average of morethan 1 but not more than about 2.1 vicinal epoxy groups per molecule;

(3) at least one material having an average of more than 1 but not morethan about 2 phenolic hydroxyl groups per molecule;

wherein components (1) and (2) are employed in quantities such that fromabout 90 to about 99.6, suitably from about 94 to about 99.6, moresuitably from about 96 to about 99.6, percent of the vicinal epoxygroups are contributed by the aromatic based epoxy resin and from about10 to about 0.4, suitably from about 6 to about 0.4, more suitably fromabout 4 to about 0.4, percent of the vicinal epoxy groups arecontributed by the aliphatic based epoxy resin; and wherein component(3) is employed in quantities such that the resultant product has an EEWof from about 1600 to about 2500, suitably from about 1650 to about2100, more suitably from about 1700 to about 1900, calculated on thebasis that the aromatic groups contained therein are free of substituentgroups even if they do in fact contain substituent groups;

(B) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a carboxylgroup, the product resulting from (A) with

(4) at least one aromatic or aliphatic monocarboxylic acid in a quantitywhich provides a ratio of moles of component (4) per epoxide groupcontained in component (1) of from about 0.033:1 to about 0.2:1,suitably from about 0.037:1 to about 0.1:1, more suitably from about0.038:1 to about 0.07:1:;

(C) optionally, reacting, in the presence of an effective quantity of acatalyst for effecting the reaction between a vicinal epoxide group anda group selected from --OH, --SH, --COOH and --CO--O--CO-- groups, theproduct resulting from (B) with a mixture comprising

(5) an aromatic based epoxy resin having an average of more than 1 butnot more than about 2.1 vicinal epoxy groups per molecule and an EEW ofnot greater than about 225, suitably not greater than about 200, moresuitably not greater than about 195, calculated on the basis of thearomatic groups being free of substituent groups whether or not they doin fact contain substituent groups; and

(6) at least one reactive material having only one group per moleculewhich is reactive with a vicinal epoxy group selected from --OH, --SH,--COOH and --CO--O--CO-- groups;

wherein component (5) is employed in an amount which provides a ratio ofvicinal epoxy groups from component (5) to vicinal epoxy groups fromcomponents (1) and (2) of from about 0.42:1 to about 0.48:1, suitablyfrom about 0.43:1 to about 0.47:1, more suitably from about 0.44:1 toabout 0.46:1: and component (6) is employed in an amount which providesfrom about 0.87 to about 1, suitably from about 0.96 to about 1, moresuitably from about 0.98 to about 1, group reactive with a vicinal epoxygroup per combined vicinal epoxy group contained in the product from (B)and component (5): and

(D) reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a carboxylgroup, the product resulting from (C) with

(7) at least one carboxyl terminated elastomer in an amount whichprovides a ratio of carboxyl groups to vicinal epoxy groups contained incomponents (1) and (2) of from about 0.0028:1 to about 0.03:1, suitablyfrom about 0.003:1 to about 0.009:1, more suitably from about 0.0035:1to about 0.008:1;

with the proviso that (a) the combined quantity of groups reactive withan epoxide group from components (3), (4), (6) and (7) cannot exceed thequantity of epoxide groups contained in components (1), (2) and (5) and(b) if step (C) is not performed, then step (D) is conducted employingthe product from step (B) instead of that from step (C): and

(II) from about 5 to about 30, suitably from about 5 to about 20, moresuitably from about 6 to about 16 percent by weight based upon thecombined weight of components (I) and (II) of the product resulting fromreacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a groupselected from --OH, --SH, --COOH and --CO--O--CO-- groups,

(8) at least one aromatic based epoxy resin having an average of morethan 1 but not ore than about 2.1 vicinal epoxy groups per molecule andan EEW of not greater than about 225, suitably not greater than about200, more suitably not greater than about 195 calculated on the basis ofthe aromatic groups being free of substituent groups whether or not theydo in fact contain substituent groups; and

(9) at least one reactant material having only one group per moleculewhich is reactive with a vicinal epoxy group selected from --OH, --SH,--COOH and --CO--O--CO-- groups; and

wherein components (8) and (9) are employed in an amount which providesa ratio of groups reactive with a vicinal epoxy group to vicinal epoxygroup of from about 0.9:1 to about 1.1:1, suitably from about 0.94:1 toabout 1:1, more suitably from about 0.96:1 to about 1:1.

A further aspect of the present invention pertains to an essentiallysolvent-free paint formulation comprising the aforementioned mixture ofcomponents (I) and (II) and at least one of (A) at least one pigment ordye or combination thereof; or (B) (1) at least one filler material (2)at least one light reflective material: or (3) a combination of (1) and(2). In these essentially solvent-free paint formulations, theaforementioned compositions require that step (C) be conducted.

Still another aspect of the present invention pertains to a solventbased paint comprising the aforementioned paint formulation and one ormore inert solvent materials. In these solvent containing paintformulations, steps (I-C) and step (II) are optional in the preparationof the aforementioned compositions employed in the paint formulation.

The present invention provides thermplastic epoxy resin formulationssuitable for use in highway marking paints which are thermally stableand which have good flexibility.

DETAILED DESCRIPTION OF THE INVENTION

The reaction enumerated in step (A) involving the mixture of thearomatic epoxy resin and aliphatic epoxy resin and the aromatichydroxyl-containing material can be conducted at any temperature betweenabout 150° C. and 225° C., usually between about 175° C. and 200° C. fora time sufficient to complete the reaction, usually between about 0.5and about 3 hours, more usually between about 1 and about 2 hours.Higher temperatures require shorter reaction times to reach the samelevel of reaction, while lower temperatures require longer reactiontimes to reach the same level of reaction In this reaction, in order toprepare a product having the desired equivalent weight, components (1),(2) and (3), are usually employed in amounts which provide a ratio ofphenolic hydroxyl groups from component (3) to vicinal epoxide groupscontained in components (1) and (2) of from about 0.8:1 to about 0.9:1,suitably from about 0.81:1 to about 0.87:1, more suitably from about0.82:1 to about 0.85:1.

When the amount of epoxide groups contributed by the aromatic basedepoxy resin is less than about 90 percent, the resultant formulatedpaint may become tacky when applied to highway surfaces in warm climatesthereby resulting in the loss of paint visibility.

When the amount of epoxide groups contributed by the aromatic basedepoxy resin is greater than about 99.6 percent, the resulting formulatedpaint will decrease in flexibility and have a shorter service life forhighway lane delineation.

When the EEW of the product produced in step (A) (the product resultingfrom the reaction of an aromatic epoxy resin and aliphatic epoxy resinand an aromatic hydroxyl-containing material), is less than about 1600,the resulting formulated paint will become tacky and tend to discolordue to highway traffic. This tendency is more predominant when theformulated paint is applied in warmer climates or in the summer time incolder climates.

When the EEW of the product produced in step (I-A) (the productresulting from the reaction of an aromatic epoxy resin and aliphaticepoxy resin and an aromatic hydroxyl-containing material) is greaterthan about 2500, the resulting formulated paint will become difficult toapply with conventional spray equipment which is currently employed.

The reaction enumerated in step (B) (the reaction between the productproduced in step (A) an the aromatic or aliphatic monocarboxylic acid)can be conducted at any temperature between about 120° C. and 190° C.,usually between about 150° C. and 190° C. for a time sufficient tocomplete the reaction, more usually between about 0.25 and about 0.6hours, usually between about 0.3 and about 0.5 hours. Highertemperatures require shorter reaction times to reach the same level ofreaction. At temperatures below about 120° C., undesirably long reactiontimes are required to complete the reaction and mechanical problemsresult with the reaction equipment due to high viscosity of the reactionmixture.

At temperatures above about 190° C., undesired side reactions may takeplace which could lead to undesirable high viscosity in the formulatedpaint.

In this reaction, in order to prepare a product having the desiredequivalent weight, component (4) is usually employed in an amount whichprovides a ratio of aromatic or aliphatic carboxyl groups from component(4) to vicinal epoxide groups contained in component (1) of from about0.033:1 to about 0.2:1, suitably from about 0.037:1 to about 0.1:1, moresuitably from about 0.038:1 to about 0..07:1.

The reaction enumerated in step (C), (the reaction between the productproduced in step (B) and the aromatic based epoxy resin and the materialhaving a group reactive with an epoxy group), can be conducted at anytemperature between about 150° C. and 210° C., usually between about175° C. and 200° C. for a time sufficient to complete the reaction,usually between about 1 and about 4 hours, more usually between about1.5 and about 2 hours. Higher temperatures require shorter reactiontimes to reach the same level of reaction, while lower temperaturesrequire longer reaction times to reach the same level of reaction Attemperatures below about 150° C., the viscosity becomes too high foreffective agitation in conventional equipment.

At temperatures above about 210° C., undesired side reactions may takeplace which could lead to high viscosity in the formulated paint.

The reaction enumerated in step (D) involving the reaction between theproduct produced in step (C) and the carboxyl terminated elastomer canbe conducted at any temperature between about 150° C. and 210° C.,usually between about 175° C. and 190° C. for a time sufficient tocomplete the reaction, usually between about 1 and about 3 hours, moreusually between about 1 and about 2 hours. Higher temperatures requireshorter reaction times to reach the same level of reaction, while lowertemperatures require longer reaction times to reach the same level ofreaction. At temperatures below about 150° C., the viscosity becomes toohigh for effective agitation in conventional reaction equipment.

At temperatures above about 210° C., undesirable side reactions may takeplace which could lead to high viscosity in the formulated paint.

The reaction between components (8) and (9) in component (II) of thepaint formulation involving the reaction between an aromatic based epoxyresin and material containing groups reactive with an epoxy resin can beconducted at any temperature between about 150° C. and 210° C., usuallybetween about 175° C. and 200° C. for a time sufficient to complete thereaction, usually between about 1 and about 4 hours, more usuallybetween about 1 and about 3 hours. Higher temperatures require shorterreaction times to reach the same level of reaction, while lowertemperatures require longer reaction times to reach the same level ofreaction. At temperatures below about 150° C., the viscosity becomes toohigh for effective agitation in conventional reaction equipment.

At temperatures above about 210° C., undesirable side reactions may takeplace which could lead to high viscosity in the formulated paint.

The amount of catalyst employed depends upon the particular componentswhich are being reacted together. However, usually, the catalyst isemployed in amounts which correspond to from about 0.0004 to about0.002, more usually from about 0.0005 to about 0.001, most usually fromabout 0.0006 to about 0.0009, mole of catalyst per epoxy group containedin the reaction mixture. At catalyst amounts below about 0.0004 mole perepoxy group, the reaction rate becomes very slow and if the catalystamount is very low, the reaction may be incomplete.

At catalyst amounts above about 0.002 mole per epoxy group, the reactionrate can become so great that the energy of the reaction cannot beremoved fast enough to stop side reactions that could lead to gellation.##STR1##

Suitable aromatic based epoxy resins which can be employed hereininclude, for example, but are not limited to those represented by thefollowing Formula I wherein each A is a divalent hydrocarbyl grouphaving from 1 to about 12, preferably from 1 to about 6 carbon atoms,--SO--, --SO₂ --, --O--, or --CO--; each R is independently hydrogen ora hydrocarbyl group having from 1 to about 4, preferably from 1 to about2 carbon atoms; each X is independently hydrogen, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 8, preferably from 1 toabout 4, carbon atoms, or a halogen, preferably chlorine or bromine: mhas an average value from about zero to about 0.5: and n has a value ofzero or 1.

Particularly suitable aromatic based epoxy resins include, for example,the diglycidyl ethers of bisphenols such as, for example, the diglycidylether of biphenol, the diglycidyl ether of bisphenol A, the diglycidylether of bisphenol F, combinations thereof and the like.

The term hydrocarbyl as employed herein means any aliphatic,cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphaticgroup, or aliphatic or cycloaliphatic substituted aromatic group.Likewise, the term hydrocarbyloxy means a hydrocarbyl group having anoxygen linkage between it and the object to which it is attached.

Suitable aliphatic based epoxy resins which can be employed hereininclude, for example, glycidyl ethers of polyhydroxyl-containingaliphatic compounds. Suitable such aliphatic based epoxy resins include,for example, but not limited to those represented by the followingFormulas II and III. ##STR2## wherein A' is a divalent aliphatichydrocarbyl group having from 2 to about 12 carbon atoms: R is asdefined above; R' is an alkyl group having from 1 to about 6 carbonatoms and n' has an average value from 1 to about 15 suitably from about1 to about 10. Particularly suitable aliphatic based epoxy resinsinclude, for example, the diglycidyl ethers of polyoxyalkylene compoundssuch as, for example, the diglycidyl ether of dipropylene glycol, thediglycidyl ether of polyoxypropylene glycol having from about 2 to about15 oxypropylene groups, the diglycidyl ether of polyoxybutene glycolhaving from about 2 to about 10 oxybutylene groups, combinations thereofand the like.

Suitable materials containing an average of more than one aromatichydroxyl groups which can be employed herein include, for example, butnot limited to those represented by the following Formula IV ##STR3##wherein A, X and n are as defined above.

Suitable aliphatic or aromatic monocarboxylic acids which can beemployed herein include, for example, those having from about 2 to about24, suitably from about 8 to about 20, more suitably from about 12 toabout 18, carbon atoms. The aliphatic or aromatic carboxylic acids mayalso contain in addition to the carboxyl group, other groups which arenot reactive with either an aliphatic hydroxyl group or an epoxy groupsuch as, for example, halogen atoms, alkyl or alkyoxy groups, and thelike. Particularly suitable monocarboxylic acids include, for example,acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, phenylacetic acid, toluic acid, combinationsthereof and the like.

Suitable anhydrides of monocarboxylic acids, those materials containinga --CO--O--CO-- group which can be employed herein include, theanhydrides of the aforementioned monocarboxylic acids.

Suitable materials having only one --OH group per molecule which can beemployed herein include, for example, monohydric aliphatic and aromaticalcohols which may be substituted with any group which does not reactwith an aliphatic or aromatic hydroxyl group or with an epoxide group,such as, for example, halogen atoms, alkyl or alkyoxy groups, and thelike. Particularly suitable monohydric alcohols include, for example,methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol,ethylene glycol monomethyl ether, propylene glycol monomethyl ether,ethylene glycol monoethyl ether, propylene glycol monoethyl ether,combinations thereof and the like. Particularly suitable monohydricaromatic alcohols include, for example phenol, alkylphenols, such as,for example, nonylphenol, t-butylphenol, cresol, combinations thereofand the like.

Suitable thiols, materials containing an --SH group, which can beemployed herein include, for example, hydrogen sulfide, thiopropane,thiopentane, combinations thereof and the like.

Suitable elastomer materials which can be employed herein include, forexample, any elastomeric material which is terminated in carboxylgroups. Particularly suitable elastomer materials include, for examplebutadiene-acrylonitrile copolymers which are terminated in carboxylgroups. Particularly suitable are the carboxyl terminatedbutadiene-acrylonitrile copolymers containing from about 20 to about 25percent by weight acrylonitrile and from about 75 to about 80 percent byweight butadiene based on the weight of acrylonitrile and butadiene. Thecarboxyl terminated butadiene-acrylonitrile copolymers have carboxycontents of from about 1.7 to about 3 percent by weight based upon totalweight of the carboxyl-containing polymer.

Suitable catalysts for effecting the reaction between the epoxy resin,the phenolic hydroxyl-containing materials and monocarboxylic acids ormonohydric alcohols or anhydrides of monocarboxylic acids include, forexample, those disclosed in U.S. Patent Nos. 3,306,872; 3,341,580;3,379,684; 3,477,990; 3,547,881; 3,948,855; 4,048,141; 4,093,650;4,131,633; 4,132,706; 4,171,420; 4,177,216; 4,302,574; 4,320,222;4,366,295 and 4,389,520 all of which are incorporated herein byreference.

Particularly suitable catalysts are those quaternary phosphonium andammonium compounds such as, for example, ethyltriphenylphosphoniumchloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphoniumiodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphoniumdiacetate (ethyltriphenylphosphonium acetate.acetic acid complex),tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,tetrabutylphosphonium iodide, tetrabutylphosphonium acetate,tetrabutylphosphonium diacetate (tetrabutylphosphonium acetate.aceticacid complex), butyltriphenylphosphonium tetrabromobisphenate,butyltriphenylphosphonium bicarbonate, benzyltrimethylammonium chlorideand tetramethylammonium hydroxide, combinations thereof and the like.

Suitable pigments, dyes or other colorants which can be employed hereininclude, any of those which will provide the coating or paint with thedesired color, such as for example, titanium dioxide, lead chromate,zinc chromate, chrome green, pthalocyamine green and blue, iron oxide,combinations thereof and the like. These pigments or colorants areemployed in quantities which provide the composition with the desiredcolor which will depend upon the particular paint formulation as well asthe particular pigment or colorant being employed. Suitable amounts ofpigments or colorants or combinations thereof include, for example fromabout 5 to about 25, suitably from about 10 to about 23, more suitablyfrom about 12 to about 20 parts by weight based upon the amount ofnon-volitile components employed in the paint or coating formulation.

Suitable fillers which can be employed herein include, for example,calcium carbonate, talc, powdered or flaked zinc or alumina, powdered orflaked glass, titanium dioxide, colloidal silica, combinations thereofand the like. The fillers are usually employed in quantities of fromabout 5 to about 30, suitably from about 5 to about 27, more suitablyfrom about 5 to about 25, percent by weight based upon the weight of thetotal formulation.

Suitable light reflective materials which can be employed hereininclude, for example, glass beads, glass flakes, glass fibers, glassbubbles, combinations thereof and the like. The light reflectivematerials are usually employed in quantities of from about 10 to about40, suitably from about 13 to about 40, more suitably from about 15 toabout 37, percent by weight based upon the weight of the totalformulation.

Suitable solvents which can be employed herein to prepare solvent bornecoatings or paints include, for example, ketones, aromatic hydrocarbons,combinations thereof and the like. Particularly suitable solventsinclude, for example, acetone, methyl ethyl ketone, methyl isobutylketone, cyclohexane, methylene chloride, combinations thereof and thelike. These solvents, when employed, are employed in quantities whichprovide the compositions with the desired application viscosity, usuallyin amounts from about 10 to about 50, suitably from about 15 to about40, more suitably from about 20 to about 35 based upon total paint orcoating formulation including the solvent.

The following examples are illustrative of the invention but are not tobe construed as to limiting the scope thereof.

MATERIALS EMPLOYED IN THE EXAMPLES AND COMPARATIVE EXPERIMENTS

EPOXY RESIN A is the diglycidyl ether of bisphenol A having an epoxideequivalent weight (EEW) of 188.

EPOXY RESIN B is the diglycidyl ether of bisphenol A having an EEW of189.

EPOXY RESIN C is the diglycidyl ether of bisphenol A having an EEW of188.6.

EPOXY RESIN D is the diglycidyl ether of polypropylene glycol having aweight average molecular weight of 425. The resultant epoxy resin had anEEW of 300.

CATALYST A is a 70 weight percent solution of ethyltriphenylphosphoniumacetate.acetic acid complex in methanol.

CATALYST B is a 70 weight percent solution of tetra-n-butylphosphoniumacetate.acetic acid complex in methanol.

ELASTOMER A is a carboxyl terminated acrylonitrile-butadiene rubbercontaining 18 weight percent acrylonitrile and 80 weight percentbutadiene and having a carboxyl equivalent weight of 2000. This materialis commercially available from B. F. Goodrich as HYCAR™ CTBN 1300X8.

FILLER A is a mixture containing 29.4 parts by weight (pbw) titaniumdioxide, 29.4 pbw calcium carbonate and 41.2 pbw 200 mesh (U. S.Standard Sieve Series) glass beads.

THICKNER A is THIXATROL™ ST commercially available from NL Chemicals.

DESCRIPTION OF TESTS Flexibility

The flexibility is determined by pressing out a thin film, 15-25 mils(0.381-0.635 mm) thick, between plastic sheets at a temperature of about200° C. After cooling overnight 0.8-1 cm×6-8 cm specimens were cut fromthe film. The coupons were then placed between the jaws of a caliper.The jaws were then moved toward each other by constant hand pressureuntil the specimen broke or is stopped. The initial length is the lengthof the specimen between the two jaws. The final length is the lengthbetween the two jaws when the specimen broke or the test is terminated.The percent elongation is calculated by the formula

    (initial length-final length)÷initial length]×100.

ABRASION

The Abrasion test is conducted on a Teledyne Taber Abraser Model No. 503using CS-10 grind stones with a 1 kg mass added to each grind stone arm.The rotation speed is 1.2 cycles per second. The grind stones arecleaned by letting the stones roll over sand paper for 10 cycles thenthe sand paper is replaced with the specimen to be evaluated. The testsample mass is determined before and after abrasion to determine themass loss. The test material is placed onto a 4 in.×4 in.×20 gauge(101.6 mm×101.6 mm×0.95 mm) cold rolled steel panel.

Reaction Product of Epoxy Resin and Stearic Acid

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 615 g (3.275 epoxy equiv.) of Epoxy Resin Aand 884.3 g (3.275 equiv.) of stearic acid. After heating to 90° C., 1.2g (0.002 mole) of Catalyst A is added. The temperature is increased to170° C. and maintained thereat for 2 hours. The resultant solid productis hereafter designated as Reaction Product A.

EXAMPLE 1

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy Resin B,2.85 g (0.0095 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C., 0.3 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.33 hours. The resultant product had an EEW of 1791. To thisadvanced epoxy resin is added 11 g (0.041 carboxyl equiv.) of stearicacid and the reaction temperature of 180° C. is maintained for 0.33hours. This product had an EEW of 2018. Then, 78.1 g (0.413 epoxyequiv.) of Epoxy Resin B and 113.2 g (0.515 equiv.) of nonyl phenol isadded and the temperature is increased to 180° C. and maintained thereatfor 1.5 hours after which, 7.2 g (0.0036 carboxyl equiv.) of Elastomer Ais added and the reaction continued for an additional 2 hours.

A portion, 21 g, of the material prepared above is mixed with 4 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is45%.

EXAMPLE 2

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy esin B,2.85 g (0.0095 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C., 0.3 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.33 hours. The resultant product had an EEW of 1791. To thisadvanced epoxy resin is added 11 g (0.041 carboxyl equiv.) of stearicacid and the reaction temperature of 180° C. is maintained for 0.33hours. The resultant product had an EEW of 2018. Then, 78.1 g (0.413epoxy equiv.) of Epoxy Resin B and 113.2 g (0.515 equiv.) of nonylphenol is added and the temperature is increased to 180° C. andmaintained thereat for 1.5 hours after which, 7.2 g (0.0036 carboxylequiv.) of Elastomer A is added and the reaction continued for anadditional 2 hours.

A portion, 23 g, of the material prepared above is mixed with 2 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is20%.

EXAMPLE 3

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy Resin B,2.89 g (0.0096 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C., 0.31 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.12 hours. The resultant product had an EEW of 1845. To thisadvanced epoxy resin is added 17 g (0.063 carboxyl equiv.) of stearicacid and the reaction temperature of 180° C. is maintained for 0.37hours. The resultant product had an EEW of 2063. Then, 78 g (0.413 epoxyequiv.) of Epoxy Resin B and 107.2 g (0.487 equiv.) of nonyl phenol isadded and the temperature is increased to 180° C. and maintained thereatfor 1.45 hours after which, 7.2 g (0.0036 carboxyl equiv.) of ElastomerA is added and the reaction continued for an additional 2 hours.

A portion, 23 g, of the material prepared above is mixed with 2 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is22%.

EXAMPLE 4

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy Resin B,2.89 g (0.0096 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C., 0.31 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.12 hours. The resultant product had an EEW of 1845. To thisadvanced epoxy resin is added 17 g (0.063 carboxyl equiv.) of stearicacid and the reaction temperature of 180° C. is maintained for 0.37hours. The resultant product had an EEW of 2063. Then, 78 g (0.413 epoxyequiv.) of Epoxy Resin B and 107.2 g (0.487 equiv.) of nonyl phenol isadded and the temperature is increased to 180° C. and maintained thereatfor 1.45 hours after which, 7.2 g (0.0036 carboxyl equiv.) of ElastomerA is added and the reaction continued for an additional 2 hours.

A portion, 21 g, of the material prepared above is mixed with 4 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is70%.

EXAMPLE 5

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 430 15 g (2.281 epoxy equiv.) of Epoxy ResinC, 3.45 g (0.012 epoxy equiv.) of Epoxy Resin D, 214.4 g (1.881 equiv.)of bisphenol A. After heating to 90° C., 1.5 g (0.0028 mole) of CatalystB is added. The temperature is increased to 185° C. and maintainedthereat for 1.17 hours. The resultant product had an EEW of 1792. Tothis advanced epoxy resin is added 24 g (0.089 carboxyl equiv.) ofstearic acid and the reaction temperature of 185° C. is maintained for0.33 hours. The resultant product had an EEW of 2113. Then, 195.9 g(1.039 epoxy equiv.) of Epoxy Resin C and 284.2 g (1.292 equiv.) ofnonyl phenol is added and the temperature is increased to 180° C. andmaintained thereat for 1.53 hours after which, 16 g (0.008 carboxylequiv.) of Elastomer A is added and the reaction continued for anadditional 2.17 hours.

A portion, 20 g, of the material prepared above is mixed with 3.5 g ofReaction Product A at 200° C., after which 15.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is50%.

EXAMPLE 6 (SOLUTION)

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 490 g (2.593 epoxy equiv.) of Epoxy Resin B,26.8 g (0.089 epoxy equiv.) of Epoxy Resin D, 236.9 g (2.078 equiv.) ofbisphenol A. After heating to 90° C., 1.3 g (0.0024 mole) of Catalyst Bis added. The temperature is increased to 190° C. and maintained thereatfor 1.28 hours. The resultant product had an EEW of 1307. To thisadvanced epoxy resin is added 138.1 g (0.511 carboxyl equiv.) of stearicacid and the reaction temperature of 190° C. is maintained for 1.03hours. The resultant product had an EEW of 8113. Then, 120.1 g (0.06carboxyl equiv.) of Elastomer A is added and the reaction continued foran additional 2.5 hours. After cooling to 130° C., 338 g of methyl ethylketone is added. The resultant product contained 75% nonvolatiles.

A portion, 47.3 g, of the material prepared above is mixed with 22.5 gof acetone, 32.7 g of Filler A and 0.1 g of Thickner A.

The above coating composition is compared to a commercially availablesolution paint, "Fast Set" available from Sherwin-Williams, by anabrasion test. This paint from Sherwin-Williams is being employed as ahighway marking paint. The results are given in the following Table I.

                  TABLE I                                                         ______________________________________                                                     EXAMPLE 6  FAST SET*                                             CYCLES       mass loss, mg                                                                            mass loss, mg                                         ______________________________________                                        0            0          0                                                     20           9.1        N.T.**                                                40           13.5       20.0                                                  60           21.7       30.8                                                  80           24.7       40.9                                                  100          32.4       51.5                                                  120          41.4       61.9                                                  140          44.9       71.3                                                  160          51.6       80.6                                                  180          58.0       90.9                                                  200          64.6       N.T.                                                  220          72.5       N.T.                                                  240          80.1       N.T.                                                  ______________________________________                                         *Not an example of the present invention.                                     **Not tested                                                             

COMPARATIVE EXPERIMENT A

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 1720.6 g (9.104 epoxy equiv.) of Epoxy ResinB, 13.8 g (0.046 epoxy equiv.) of Epoxy Resin D, 871 g (7.64 equiv.) ofbisphenol A. After heating to 90° C., 3 g (0.006 mole) of Catalyst B isadded. The temperature is increased to 150° C., the contents allowed toexotherm to 203° C. and then cooled to 185° C. and maintained thereatfor 1.07 hour. The resultant product had an EEW of 1807. To thisadvanced epoxy resin is added 48.2 g (0.178 carboxyl equiv.) of stearicacid and the reaction temperature of 185° C. is maintained for 1.95hours. The resultant product had an EEW of 2216. A portion, 289.9 g, ofthis material (containing 0.131 epoxy equiv.) is placed into anotherreaction vessel containing 84.7 g (0.448 epoxy equiv.) of Epoxy Resin Band 125.5 g (0.57 equiv.) of nonyl phenol. The temperature is increasedto 180° C. and maintained thereat for 1.5 hours, after which 7.6 g(0.004 carboxyl equiv.) of Elastomer A is added and the reactioncontinued for an additional 2.33 hours.

A portion, 23 g, of the material prepared above is mixed with 2 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is<1%.

COMPARATIVE EXPERIMENT B

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 1720.6 g (9.104 epoxy equiv.) of Epoxy ResinB, 13.8 g (0.046 epoxy equiv.) of Epoxy Resin D, 871 g (7.64 equiv.) ofbisphenol A. After heating to 90° C., 3 g (0.006 mole) of Catalyst B isadded. The temperature is increased to 150° C., the contents allowed toexotherm to 205° C. and then cooled to 185° C. and maintained thereatfor 1 hour. The resultant product had an EEW of 1770. To this advancedepoxy resin is added 24.2 g (0.089 carboxyl equiv.) of stearic acid andthe reaction temperature of 185° C. is maintained for 1.5 hours. Theresultant product had an EEW of 2018. A portion, 280 g, of this material(containing 0.139 epoxy equiv.) is placed into another reaction vesselcontaining 81.9 g (0.433 epoxy equiv.) of Epoxy Resin B and 124.3 g(0.565 equiv.) of nonyl phenol. When the temperature reached 120° C.,0.5 g (0.0009 mole) of Catalyst B is added. The temperature is increasedto 180° C. and maintained thereat for 1.83 hours, after which 7.5 g(0.004 carboxyl equiv.) of Elastomer A is added and the reactioncontinued for an additional 1.5 hours.

A portion, 21 g, of the material prepared above is mixed with 4 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is 2%.

COMPARATIVE EXPERIMENT C

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy Resin B,2.9 g (0.0097 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C., 0.31 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.02 hours. The resultant product had an EEW of 1777. To thisadvanced epoxy resin is added 78.1 g (0.413 epoxy equiv.) of Epoxy ResinB and 7.2 g (0.0036 carboxyl equiv.) of Elastomer A is added and thereaction continued for an additional 2 hours.

COMPARATIVE EXPERIMENT D

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 1720.6 g (9.104 epoxy equiv.) of Epoxy ResinB, 13.8 g (0.046 epoxy equiv.) of Epoxy Resin D, 871 g (7.64 equiv.) ofbisphenol A. After heating to 90° C., 3 g (0.006 mole) of Catalyst B isadded. The temperature is increased to 150° C., the contents allowed toexotherm to 203° C. and then cooled to 185° C. and maintained thereatfor 1.07 hours. The resultant product had an EEW of 1807. To thisadvanced epoxy resin is added 48.2 g (0.178 carboxyl equiv.) of stearicacid and the reaction temperature of 185° C. is maintained for 1.95hours. This product had an EEW of 2216. A portion, 289.9 g, of thismaterial (containing 0.131 epoxy equiv.) is placed into another reactionvessel containing 84.7 g (0.448 epoxy equiv.) of Epoxy Resin B and 125.5g (0.57 equiv.) of nonyl phenol. After mixing, at a temperature of 98°C., 0.5 g (0.0009 mole) of catalyst B is added. The temperature isincreased to 180° C. and maintained thereat for 1.5 hours, after which7.6 g (0.004 carboxyl equiv.) of Elastomer A is added and the reactioncontinued for an additional 2.33 hours.

A portion, 21 g, of the material prepared above is mixed with 4 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is 7%.

COMPARATIVE EXPERIMENT E

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 1720.6 g (9.104 epoxy equiv.) of Epoxy ResinB, 13.8 g (0.046 epoxy equiv.) of Epoxy Resin D, 871 g (7.64 equiv.) ofbisphenol A. After heating to 90° C., 3 g (0.006 mole) of Catalyst B isadded. The temperature is increased to 150° C., the contents allowed toexotherm to 205° C. and then cooled to 185° C. and maintained thereatfor 1 hour. The resultant product had an EEW of 1770. To this advancedepoxy resin is added 24.2 g (0.089 carboxyl equiv.) of stearic acid andthe reaction temperature of 185° C is maintained for 1.5 hours. Theresultant product had an EEW of 2018. A portion, 280 g, of this material(containing 0.139 epoxy equiv.) is placed into another reaction vesselcontaining 82.2 g (0.435 epoxy equiv.) of Epoxy Resin B and 123.6 g(0.562 equiv.) of nonyl phenol. After mixing, and increasing thetemperature to 145° C., 0.5 g (0.0009 mole) of catalyst B is added. Thetemperature is increased to 180° C. and maintained thereat for 1.58hours, after which 15.3 g (0.0077 carboxyl equiv.) of Elastomer A isadded and the reaction continued for an additional 2 hours.

A portion, 21.5 g, of the material prepared above is mixed with 3.5 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is 5%.

COMPARATIVE EXPERIMENT F

To a reaction vessel equipped with a means for stirring, heating controland nitrogen purge is added 172 g (0.91 epoxy equiv.) of Epoxy Resin B,2.84 g (0.0095 epoxy equiv.) of Epoxy Resin D, 87.5 g (0.767 equiv.) ofbisphenol A. After heating to 90° C, 0.3 g (0.0006 mole) of Catalyst Bis added. The temperature is increased to 180° C. and maintained thereatfor 1.33 hours. The resultant product had an EEW of 1720. To thisadvanced epoxy resin is added 7.2 g (0.027 carboxyl equiv.) of stearicacid and the reaction temperature of 180° C. is maintained for 0.33hours. The resultant product had an EEW of 2131. Then, 78.4 g (0.415epoxy equiv.) of Epoxy Resin B and 117.6 g (0.535 equiv.) of nonylphenol is added and the temperature is increased to 180° C. andmaintained thereat for 1.5 hours after which, 7.2 g (0.0036 carboxylequiv.) of Elastomer A is added and the reaction continued for anadditional 2.17 hours.

A portion, 23.5 g, of the material prepared above is mixed with 1.5 g ofReaction Product A at 200° C., after which 16.7 g of Filler A is addedand the mixture blended. The flexibility of the resultant product is 4%.

EXAMPLE 7

The thermal stability is determined for Example 1 and ComparativeExperiment C. The stability is determined by mixing the resins to becompared with a second resin and determining the thermal stability onthe resin blend.

THERMAL STABILITY TEST

The thermal stability test is run using a Brookfield Thermosel set at232° C. The resin mixture (9 g) ws placed into the Thermosel cup whichis then placed into the viscometer oven. When the resin mixture isfluid, the spindle (No. 21) is lowered into the resin and the viscometermotor started. The viscosity is determined and recorded as the initialviscosity. The resin mixture is left in the viscosity oven for 4 hoursand the viscosity measured again and recorded as the final viscosity.The results are given in Table II.

                  TABLE II                                                        ______________________________________                                        SAM-                                                                          PLE                         INITIAL  FINAL                                    NUM-  RESIN 1    RESIN 2    VISCOSITY                                                                              VISCOSITY                                BER   Type/grams Type/grams cps/Pa.s cps/Pa.s                                 ______________________________________                                        A*    Comp. Exp. Epoxy resin                                                                              940/0.94 1625/1.625                                     C/23.5     B/1.5                                                        B     Example 1/21                                                                             Reaction   196/0.196                                                                              201/0.201                                                 Product A/4                                                  ______________________________________                                         *Not an example of the present invention.                                

We claim:
 1. A thermally stable, flexible thermoplastic epoxy resinresulting from(A) reacting, in the presence of an effective quantity ofa catalyst for effecting the reaction between a vicinal epoxide and anaromatic hydroxyl group, a mixture comprising(1) at least one aromaticbased epoxy resin having an average of more than 1 but not more thanabout 2.1 vicinal epoxy groups per molecule; (2) at least one aliphaticbased epoxy resin having an average of more than 1 but not more thanabout 2.1 vicinal epoxy groups per molecule; (3) at least one materialhaving an average of more than 1 but not more than about 2 phenolichydroxyl groups per molecule; wherein components (1) and (2) areemployed in quantities such that from about 90 to about 99.6 percent ofthe vicinal epoxy groups are contributed by the aromatic based epoxyresin and from about 10 to about 0.4 percent of the vicinal epoxy groupsare contributed by the aliphatic based epoxy resin; and whereincomponent (3) is employed in quantities such that the resultant producthas an epoxide equivalent weight of from about 1600 to about 2500,calculated on the basis that the aromatic groups contained therein arefree of substituent groups even if they do in fact contain substituentgroups; (B) reacting, in the presence of an effective quantity of acatalyst for reacting a vicinal epoxide group with a carboxylic acidgroup, the product resulting from (A) with(4) at least one aromatic oraliphatic monocarboxylic acid in a quantity which provides a ratio ofmoles of component (4) per epoxide group contained in component (1) offrom about 0.033:1 to about 0.2:1; (C) reacting, in the presence of aneffective quantity of a catalyst for effecting the reaction between avicinal epoxide group and a group selected from --OH, --SH, --COOH or--CO--O--CO-- groups, the product resulting from (B) with a mixturecomprising(5) an aromatic based epoxy resin having an average of morethan 1 but not more than about 2.1 vicinal epoxy groups per molecule andan epoxide equivalent weight of not greater than about 225, suitably notgreater than about 200, more suitably not greater than about 195,calculated on the basis of the aromatic groups being free of substituentgroups whether or not they do in fact contain substituent groups; and(6) a reactive material having only one group per molecule which isreactive with a vicinal epoxy group selected from --OH, --SH, --COOH or--CO--O--CO-- groups; wherein component (5) is employed in an amountwhich provides a ratio of vicinal epoxy groups from component (5) to thecombined amount epoxy groups contained in components (1) and (2) of fromabout 0.42:1 to about 0.48:1: and component (6) is employed in an amountwhich provides from about 0.87 to about 1 group reactive with a vicinalepoxy group per combined vicinal epoxy group contained in the productfrom (B) and component (5); and (D) reacting, in the presence of aneffective quantity of a catalyst for effecting the reaction between avicinal epoxy group and a carboxyl group, the product resulting from (C)with(7) a carboxyl terminated elastomer in an amount which provides aratio of carboxyl groups per vicinal epoxy group contained in components(1) and (2) of from about 0.0028:1 to about 0.03:1;with the proviso thatthe combined quantity of groups reactive with an epoxide group fromcomponents (3), (4), (6) and (7) cannot exceed the combined quantity ofepoxide groups contained in components (1), (2) and (5) and.
 2. An epoxyresin of claim 1 wherein(i) components (1) and (2) are employed inquantities that from about 94 to about 99.6 percent of the vicinal epoxygroups are contributed by the aromatic based epoxy resin and from about6 to about 0.4, percent of the vicinal epoxy groups are contributed bythe aliphatic based epoxy resin; (ii) components (1), (2) and (3) areemployed in quantities such that the resultant product has an epoxideequivalent weight of from about 1650 to about 2100 calculated on thebasis of the aromatic groups being free of substituent groups whether ornot they do in fact contain substituent groups; (iii) component (4) isemployed in a quantity which provides a ratio of moles of component (4)per epoxide group contained in component (1) of from about 0.037:1 toabout 0.1:1; (iv) component 5 is employed in an amount which provides aratio of vicinal epoxy groups from component (5) to vicinal epoxy groupsfrom component (1) of from about 0.43:1 to about 0.47:1; (v) component 6is employed in an amount which provides from about 0.96 to about 1 groupreactive with a vicinal epoxy group per combined vicinal epoxy groupcontained in the product from (B) and component (5); and (vi) component7 is employed in an amount which provides a ratio of carboxyl groups pervicinal epoxy group contained in components 1 and 2 of from about0.003:1 to about 0.009:1.
 3. An epoxy resin of claim 2 wherein(i)components (1) and (2) are employed in quantities such that from about96 to about 99.6 percent of the vicinal epoxy groups are contributed bythe aromatic based epoxy resin and from about 4 to about 0.4, percent ofthe vicinal epoxy groups are contributed by the aliphatic based epoxyresin; (ii) components (1), (2) and (3) are employed in quantities suchthat the resultant product has an epoxide equivalent weight of fromabout 1700 to about 1900 calculated on the basis of the aromatic groupsbeing free of substituent groups whether or not they do in fact containsubstituent groups; (iii) component (4) is employed in a quantity whichprovides a ratio of moles of component (4) per epoxide group containedin component (1) of from about 0.038:1 to about 0.07:1; (iv) component 5is employed in an amount which provides a ratio of vicinal epoxy groupsfrom component (5) to vicinal epoxy groups from component (1) of fromabout 0.44:1 to about 0.46:1; (v) component 6 is employed in an amountwhich provides from about 0.98 to about 1 group reactive with a vicinalepoxy group per combined vicinal epoxy group contained in the productfrom (B) and component (5); and (vi) component 7 is employed in anamount which provides a ratio of carboxyl groups per vicinal epoxy groupcontained in component 1 of from about 0.0035:1 to about 0.008:1.
 4. Anepoxy resin of claims 1, 2 or 3 wherein(i) component (1) is a diglycidylether of a bisphenol; (ii) component (2) is a diglycidyl ether of apolyoxyalkylene glycol; (iii) component (3) is a bisphenol; (iv)component (4) is an aliphatic monocarboxylic acid; (v) component (5) isa diglycidyl ether of a bisphenol; (vi) component (6) is an alkylphenol; and (vii) component (7) is a butadiene-acrylonitrile copolymer.5. An epoxy resin of claim 4 wherein(i) component (1) is a diglycidylether of bisphenol A; (ii) component (2) is a diglycidyl ether of apolyoxypropylene glycol; (iii) component (3) is bisphenol A; (iv)component (4) is stearic acid; (v) component (5) is a diglycidyl etherof bisphenol A; (vi) component (6) is nonyl phenol; and (vii) component(7) is a carboxyl-containing copolymer containing from about 20 to about25 percent by weight acrylonitrile and from about 75 to about 80 percentby weight butadiene based upon the combined weight of acylonitrile andbutadiene; and from about 1.7 to about 3 percent by weight of carboxylgroups based upon the total weight of the carboxyl-containing polymer.6. A paint formulation comprising a mixture of claim 4 and (a) at leastone pigment or dye: (b) at least one filler material (c) at least onelight reflective material; or (d) any combination of two or more membersselected from (a), (b) or (c).
 7. A paint formulation of claim 6 whereinboth components (a) and (c) are present.
 8. A paint formulation of claim7 wherein component (c) is glass beads.
 9. A paint formulationcomprising a mixture of claim 5 and (a) at least one pigment or dye: (b)at least one filler material: (c) at least one light reflectivematerial: or (d) any combination of two or more members selected from(a), (b) or (c).
 10. A paint formulation of claim 9 wherein bothcomponents (a) and (c) are present.
 11. A paint formulation of claim 10wherein component (c) is glass beads.
 12. A paint formulation comprisingthe formulation of claim 6 and one or more inert solvents.
 13. A paintformulation of claim 12 wherein said solvent is acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexane, methylene chloride, or acombination thereof.
 14. A paint formulation comprising the formulationof claim 7 and one or more inert solvents.
 15. A paint formulation ofclaim 14 wherein said solvent is acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexane, methylene chloride, or a combinationthereof.
 16. A paint formulation comprising the formulation of claim 8and one or more inert solvents.
 17. A paint formulation of claim 16wherein said solvent is acetone, methyl ethyl ketone, methyl isobutylketone, cyclohexane, methylene chloride, or a combination thereof.
 18. Apaint formulation comprising the formulation of claim 9 and one or moreinert solvents.
 19. A paint formulation of claim 18 wherein said solventis acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane,methylene chloride, or a combination thereof.
 20. A paint formulationcomprising the formulation of claim 10 and one or more inert solvents.21. A paint formulation of claim 20 wherein said solvent is acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, methylenechloride, or a combination thereof.
 22. A paint formulation comprisingthe formulation of claim 11 and one or more inert solvents.
 23. A paintformulation of claim 22 wherein said solvent is acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexane, methylene chloride, or acombination thereof.
 24. A process for preparing a thermally stable,flexible thermoplastic epoxy resin which comprises(A) reacting, in thepresence of an effective quantity of a catalyst for effecting thereaction between a vicinal epoxy group and an aromatic hydroxyl group, amixture comprising(1) at least one aromatic based epoxy resin having anaverage of more than 1 but not more than about 2.1 vicinal epoxy groupsper molecule; (2) at least one aliphatic based epoxy resin having anaverage of more than 1 but not more than about 2.1 vicinal epoxy groupsper molecule; (3) at least one material having an average of more than 1but not more than about 2 phenolic hydroxyl groups per molecule; whereincomponents (1) and (2) are employed in quantities such that from about90 to about 99.6 percent of the vicinal epoxy groups are contributed bythe aromatic based epoxy resin and from about 10 to about 0.4 percent ofthe vicinal epoxy groups are contributed by the aliphatic based epoxyresin; and wherein component (3) is employed in quantities such that theresultant product has an epoxide equivalent weight of from about 1600 toabout 2500, calculated on the basis that the aromatic groups containedtherein are free of substituent groups even if they do in fact containsubstituent groups; (B) reacting, in the presence of an effectivequantity of a catalyst for effecting the reaction between a vicinalepoxy group and a carboxyl group, the product resulting from (A) with(4)at least one aromatic or aliphatic monocarboxylic acid in a quantitywhich provides a ratio of moles of component (4) per epoxide groupcontained in component (1) of from about 0.033:1 to about 0.2:1; (C)reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a groupselected from --OH, --SH, --COOH or --CO--O--CO-- groups, the productresult from (B) with a mixture comprising(5) an aromatic based epoxyresin having an average of more than 1 but not more than about 2.1vicinal epoxy groups per molecule and an epoxide equivalent weight ofnot greater than about 225, suitably not greater than about 200, moresuitably not greater than about 195, calculated on the basis of thearomatic groups being free of substituent groups whether or not they doin fact contain substituent groups; and (6) a material having only onegroup per molecule which is reactive with a vicinal epoxy group selectedfrom --OH, --SH, --COOH or --CO--O--CO-- groups; wherein component (5)is employed in an amount which provides a ratio of vicinal epoxy groupsfrom component (5) to the combined amount epoxy groups contained incomponents (1) and (2) of from about 0.42:1 to about 0.48:1: andcomponent (6) is employed in an amount which provides from about 0.87 toabout 1 group reactive with a vicinal epoxy group per combined vicinalepoxy group contained in the product from (B) and component (5); and (D)reacting, in the presence of an effective quantity of a catalyst foreffecting the reaction between a vicinal epoxide group and a carboxylgroup, the product resulting from (C) with(7) a carboxyl terminatedelastomer in an amount which provides a ratio of carboxyl groups pervicinal epoxy group contained in components (1) and (2) of from about0.0028:1 to about 0.03:1;with the proviso that the combined quantity ofgroups reactive with an epoxide group from components (3), (4), (6) and(7) cannot exceed the combined quantity of epoxide groups contained incomponents (1), (2) and (5).